Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
  • C08F226/10—N-Vinyl-pyrrolidone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
  • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/01—Aerosol hair preparation

Definitions

• the present invention relates to a terpolymer of vinylpyrrolidone, tert-butyl (meth)acrylate and acrylic or methacrylic acid, its use in hair treatment agents, and compositions for the hair cosmetics sector which contain these terpolymers.
• Film-forming resins based on carboxyl-containing vinylmonomers and (meth)acrylates and/or vinyl acetate have long been used, particularly for hair sprays in which halohydrocarbons, such as fluorohydrocarbons, are used as propellants.
• halohydrocarbons such as fluorohydrocarbons
• the partial or complete neutralization improves the water solubility or dispersability of the resin used and makes them easier to remove from the hair during washing. Neutralization makes it possible to have an advantageous effect on the flexibility of the films sprayed on.
• halohydrocarbons in aerosol hair spray formulations are increasingly being replaced with pure hydrocarbons, such as propane or butane.
• pure hydrocarbons such as propane or butane.
• the use of these hydrocarbons as propellants gives rise to a number of problems, the reduced solubility of the hair spray resins, for example in alcoholic solution in the presence of these hydrocarbons as propellants, playing a particular role.
• carboxylated resins are as a rule readily soluble in anhydrous alcohol/halohydrocarbon spray formulations, their reduced solubility in the alcohol/hydrocarbon formulations which have recently come into use may make them unacceptable for modern hair spray formulations.
• U.S. Pat. No. 3,405,084 describes neutralized terpolymers for hair spray formulations which consist of from 20 to 75% by weight of vinylpyrrolidone, from 20 to 70% by weight of an alkyl ester of acrylic or methacrylic acid, where the ester alcohol has a saturated straight-chain or branched radical of 1 to 10 carbon atoms, and from 3 to 25% by weight of acrylic acid or methacrylic acid.
• the terpolymer obtained possesses optimum solubility, in particular in the alcohol/hydrocarbon propellant mixtures used in hair sprays, as well as optimum film-forming properties, which could not be foreseen, and meets the requirements set. This is particularly true since some of the copolymers with n-butyl and isobutyl acrylate and methacrylate have proven unsatisfactory in practical tests to determine their compatibility with propellant gases and curl retention.
• novel terpolymers are useful as film formers, in particular for hair sprays, but may also be used in hair-setting compositions, hair foams or hair gels.
• the novel terpolymers are advantageously in a form which is partly or completely neutralized by an organic amine, from 5 to 100%, preferably from 50 to 90%, of the carboxyl groups being neutralized.
• the carboxyl groups are preferably neutralized with an alkanolamine from the series consisting of the mono-, di- and trialkanolamines where the alkanol radical is of 2 to 5 carbon atoms, such as mono-, di- or triethanolamine, mono-, di- or tripropanolamine or 2-amino-2-methylpropanol, or an alkanediolamine where the alkanediol radical is of 2 to 4 carbon atoms, such as 2-amino-2-methylpropane-1,3-diol or 2-amino-2-ethylpropane-1,3-diol, or by di-(methoxyethyl)-amine or a primary, secondary or tertiary alkylamine having a total of 5 to 10 carbon atom
• 2-amino-2-methylpropanol, triisopropanolamine and 2-amino-2-ethylpropane-1,3-diol are preferred.
• the present invention furthermore relates to a hair treatment agent which contains, as a film former, a novel terpolymer in the partly or completely neutralized form, in an amount of from 0.5 to 15, preferably from 1 to 10, %, based on the total weight, and the use of the novel terpolymers in hair treatment agents.
• the particularly preferred formulation is a hair spray composition which contains from 0.5 to 15% by weight of a novel terpolymer, from 5 to 100%, preferably from 50 to 90%, of whose carboxyl groups have been neutral with one of the abovementioned organic amines, from 10 to 95% by weight of a solvent selected from the group consisting of acetone, ethanol, propanol, isopropanol, 1-methoxypropan-2-ol and mixtures of these, and from 5 to 90% by weight of a propellant selected from the group consisting of propane, n-butane, isobutane, 2,2-dimethylpropane, isopentane, dimethyl ether and mixtures of these.
• a solvent selected from the group consisting of acetone, ethanol, propanol, isopropanol, 1-methoxypropan-2-ol and mixtures of these
• a propellant selected from the group consisting of propane, n-butane, isobutane, 2,2-d
• This hair spray composition may also contain from 0.1 to 5% by weight of water or from 1 to 35% by weight of methylene chloride or trichloromethane, the percentages being based on the total weight.
• compositions contain:
• novel terpolymers of the compositions stated above and described in detail in the Examples are advantageously and preferably used in hair sprays of the above general formulation.
• terpolymers which contain methacrylic acid and at the same time are the most compatible with propellant gas are recommended.
• the water solubility of the terpolymers used may play an important role in formulations which contain water as a solvent.
• Such formulations are, in particular, hair setting compositions, hair foams and hair gels.
• a solvent selected from the group consisting of acetone, ethanol (96% pure), propanol, isopropanol, 1-methoxypropan-2-ol and mixtures of these, and
• a preferred hair setting composition is predominantly aqueous and contains from 2 to 10% by weight of the terpolymer defined above and from 60 to 98% by weight of water and, where relevant, one of the abovementioned solvents or mixtures of these to make up to 100% by weight.
• the preparation of aqueous formulations is a particular advantage of the present invention.
• a solvent from the group consisting of acetone, ethanol, propanol, isopropanol, 1-methoxypropan-2-ol and mixtures of these, and
• a propellant selected from the group consisting of propane, n-butane, isobutane, 2,2-dimethylpropane, isopentane, dimethyl ether and mixtures of these, 25:75 propane/butane mixtures being preferred.
• foam-forming and foam-stabilizing assistants familiar to the skilled worker are added to these compositions.
• examples are Ceteareth 25 or 11, Nonoxynol 14 or 10 and Cocamide DEA (cf. CTFA, Cosmetics Ingredient Dictionary, 3rd edition 1982).
• aqueous hair treatment agents constitute a preferred subject of the present invention.
• Particularly suitable for aqueous hair formulations are the terpolymers composed of vinylpyrrolidone, tert-butyl acrylate and methacrylic acid, these terpolymers being used in an amount from 2 to 10% by weight, based on the total weight.
• the novel copolymers are prepared by conventional free radical copolymerization, preferably by solution polymerization in a monohydric lower alcohol of 1 to 4 carbon atoms, in particular ethanol or isopropanol.
• the conventional peroxides such as benzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide or tert-butyl hydroperoxide and azo initiators, such as azobisisobutyronitrile, are used as initiators, advantageously in amounts of from 0.3 to 2.0% by weight, based on the weight of the monomers.
• the solvent can be removed in a conventional manner, for example by spray-drying.
• the novel terpolymers have K values of from 10 to 60, preferably from 15 to 50, measured in 2% strength by weight solution in ethanol at 25° C. in the acid form.
• the K value is a measure of the molecular weight (Fikentscher, Cellulosechemie 13 (1932), 58-64 and 71-74).
• the remaining monomer solution is added in the course of about 5 hours and at the same time the remaining initiator solution is introduced in the course of about 7 hours, the internal temperature being kept at about 80°-82° C. with gentle boiling. When the addition is complete, polymerization is continued for about 1 hour at these temperatures.
• a monomer mixture of the composition shown in Examples 9 to 12 in Table 2 100 parts are dissolved in 24 parts of ethanol. 10% by weight of this monomer solution, 10% by weight of the prepared initiator solution consisting of 0.8 part of tert-butyl perpivalate and 27 parts of ethanol, and 50 parts of ethanol are initially taken and heated to about 75° C. in a stirred flask equipped with a reflux condenser and two dropping funnels.
• the remaining monomer solution is added in the course of 3 hours and at the same time the remaining initiator solution is introduced in the course of about 6 hours, the internal temperature being kept at about 78°-80° C.
• terpolymers with n-, sec- and isobutyl acrylate and n-, sec- and isobutyl methacrylate are prepared under the conditions of Example 1, these terpolymers being shown in the Table and described in U.S. Pat. No. 3,405,084.
• the compatibility with the propellant mixture propane/butane in a weight ratio of 40:60 indicates the amount, in % by weight, of this propellant mixture which can be used in an ethanolic hair spray solution containing 3% by weight of terpolymer and having a degree of neutralization of 75%, in order for the solution obtained still to be clear at 0° C.
• a compatibility of, for example, 71% with propellant gas means that a 3% strength by weight solution containing 71% by weight of propellant gas, the remainder to 100% by weight being ethanol, gives a clear solution at 0° C.
• the curl retention is a measure of the hair setting effect. It is measured in a model experiment using curls produced by a conventional water wave in hair about 15 cm long which has been sprayed for 4 seconds from a distance of 10 cm with 2% strength by weight spray solution containing a resin shown in Table 1 or 2 and having a degree of neutralization of 75%. After the suspended curls have been treated for 5 hours in a conditioned chamber (25° C., 90% relative humidity), the relative deformation (extension) of the curls, based on the original shape, is determined. A high value indicates a good setting effect, ie. 100% would denote retention of the original shape of the suspended curls while 0% would represent fully extended hair.
• Comparative Example 7 is at the lower limit of usefulness. It was not expected that the novel terpolymers with tert-butyl acrylate and tert-butyl methacrylate would give the best values in the combination of the properties investigated. The compositions in which acrylic acid is replaced with methacrylic acid give even better results. Examples of formulations:

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• Life Sciences & Earth Sciences (AREA)
• General Health & Medical Sciences (AREA)
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• Animal Behavior & Ethology (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
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• Cosmetics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1986
  • 1986-08-18 DE DE19863627970 patent/DE3627970A1/de not_active Withdrawn
• 1987
  • 1987-07-23 US US07/076,874 patent/US4767613A/en not_active Expired - Fee Related
  • 1987-08-04 CA CA000543655A patent/CA1306417C/fr not_active Expired - Lifetime
  • 1987-08-12 ES ES87111649T patent/ES2024462B3/es not_active Expired - Lifetime
  • 1987-08-12 DE DE8787111649T patent/DE3773084D1/de not_active Expired - Lifetime
  • 1987-08-12 EP EP87111649A patent/EP0257444B1/fr not_active Expired - Lifetime
  • 1987-08-14 JP JP62201961A patent/JPS6348315A/ja active Pending

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